Novel amine-containing copolymers and their use

ABSTRACT

This invention relates to novel polymeric compositions which are useful for water treatment. These novel compositions are comprised of a polymers of α,β ethylenically unsaturated monomer(s), preferably containing carboxylic acid or carboxylic amide functionalities, and amine-containing allyl ether monomers.

This application is a continuation-in-part of U.S. Ser. No. 37,484 filedApr. 13, 1987, which is a continuation of Ser. No. 64,049 filed May 16,1986 (now U.S. Pat. No. 4,659,481), which in turn is a continuation ofSer. No. 545,563 filed Oct. 26, 1983 (now abandoned).

FIELD OF THE INVENTION

This invention relates to novel polymeric compositions which are usefulfor water treatment. These novel compositions are comprised of polymersof α,β ethylenically unsaturated monomer(s), preferably containingcarboxylic acid or carboxylic amide functionalities, andamine-containing allyl ether monomers.

BACKGROUND OF THE INVENTION

The present invention is directed to novel polymeric compositionscontaining pendant functional groups. The polymers are useful for abroad range of water treatment applications. They can be used to controlthe formation and deposition of scale imparting compounds in watersystems such as cooling, boiler, gas scrubbing, and pulp and papermanufacturing systems. They will also find utility as corrosioninhibitors, as well as functioning as chelating agents for variousmetallic ions in solution.

As described comprehensively in U.S. Pat. No. 4,497,713, scaling andcorrosion in cooling waters is a major problem. The term "cooling water"is applied wherever water is circulated through equipment to absorb andcarry away heat. This definition includes air conditioning systems,engine jacket systems, refrigeration systems, as well as the multitudeof industrial heat exchange operations.

In a cooling water system employing a cooling tower, water is circulatedthrough the heat transfer equipment and subsequently cooled byevaporation of a part of the circulating water as the water is passedover the cooling tower. By virtue of the evaporation which takes placein cooling, the dissolved and suspended solids in the water becomeconcentrated. The circulatng water becomes more concentrated than themake-up water due to this evaporation loss.

The make-up water employed for recirculating systems is obtained fromsurface or well water sources. These waters normally contain a varietyof dissolved salts, the abundance and composition of which depend on thesource of the water. Generally the make-up water will contain apreponderance of the alkaline earth metal cations, primarily calcium andmagnesium, and sometimes iron, and such anions as silicate, sulfate,bicarbonate, and carbonate. As the water is concentrated by theevaporative process, precipitation of a salt will occur whenever thesolubility of the particular cation/anion combination is exceeded. Ifthe precipitation occurs at a metal surface, and adheres to it, theresultant deposit is referred to as scale. Some of the factors whichaffect scale are temperature, rate of heat transfer, water velocity,dissolved solids concentration, cycles of concentration, systemretention, and pH of the water.

Preventing the corrosion and scaling of industrial heat transferequipment is essential to the efficient and economical operation of acooling system.

Excessive corrosion of metallic surfaces can cause the premature failureof process equipment, necessitating downtime for the repair orreplacement.

In addition, the buildup of corrosion products on heat transferequipment impedes water flow and reduces heat transfer efficiency,thereby limiting production or requiring downtime for cleaning.Reduction in efficiency will also result from scaling deposition whichretards heat transfer and hinders water flow.

Scale can also cause rapid localized corrosion and subsequentpenetration of metallic surfaces through the formation of differentialoxygen concentration cells. The localized corrosion resulting fromdifferential oxygen cells originating from deposits is commonly referredto as "under-deposit corrosion."

With regard to boiler systems, and as described comprehensively in U.S.Pat. No. 4,288,327, the formation of scale and sludge deposits on boilerheating surfaces is the most serious water problem encountered in steamgeneration. Although external treatment is utilized in an attempt toremove calcium and magnesium ions from the feed water, scale formationdue to residual hardness (calcium and magnesium salts) is normallyexperienced. Accordingly, internal treatment is necessary to prevent,reduce, or inhibit formation of the scale-imparting compounds and theirdeposition.

Other scale-forming species (phosphate, sulfate, and silicate salts, forexample) can form complex insoluble salts, depositing as boiler scale.

Therefore, there is a need in industrial water treatment for materialswhich can prevent or inhibit the formation of scale and deposits on heattransfer surfaces in boiler systems, and the like.

DESCRIPTION OF THE PRIOR ART

Domba, U.S. Pat. No. 3,989,636, describes novel amino acid-epihalohydrincopolymers with chelating properties. These polymers differ chemicallyfrom those of the present invention. The '636 polymers are of thecondensation type, whereas the instant polymers are prepared by additionpolymerization. This results, in the case of the instant invention, inpolymeric chains containing a carbon backbone, whereas in the '636patent, a backbone containing nitrogen atoms is produced. The molecularweights contemplated by the '636 patent are furthermore well outside themolecular weight range of the novel polymers of the present invention.In addition, the instant polymers are significantly more effective asscale control agents in boiler water treatment, since they reduce scalemore effectively than the '636 polymers at dosages far lower than thespecific '636 polymers described.

Quinlan, U.S. Pat. No. 3,799,893, describes phosphorous containingcompounds which are described as useful for inhibiting scale formation.The compounds described are methylene phosphonates of glycidyl reactedpolyalkylene polyamines. These materials are chemically significantlydifferent from the instant polymers: the '893 compounds do not containcarboxylic acid groups; the '893 best mode compounds are not polymers;and, the '893 compounds have nitrogen in the backbone of the structure.For these reasons, the '893 compounds are not considered to be pertinentprior art. Furthermore, although the test conditions for determiningscale inhibition are substantially different in '893 and the instantinvention, the instant polymers appear to be more effective in scaleinhibition at substantially lower dosages than the best mode '893compounds.

Boffardi, et. al., U.S. Pat. No. 4,018,702 disclose scale and corrosioninhibiting compositions which comprise amine adducts of polymaleicanhydride. The instant invention differs from the '702 patent in anumber of significant aspects. The '702 polymers are amides, whereas inthe instant invention the amine group is attached to the polymeric chainthrough a hydrogen-substituted carbon. The instant polymers aresignificantly more stable in an aqueous environment than the '702polymers, which would be expected to lose the amine functionality fromthe polymer chain through hydrolysis. Such hydrolysis is difficult withthe instant polymers. Furthermore, the best mode polymers of the '702patent have a molecular weight of only about 200-300 (Example 1 of '702,the only disclosed example of the preparation of polymer). The molecularweights of the present polymer fall within the range of about 1,000 toabout 1,000,000, with the most preferred range being from about 1,500 toabout 25,000. Thus, the instant polymers are well outside the range ofthe '702 polymers. Therefore, the '702 polymers are not considered to bepertinent prior art to the instant invention.

D'Alelio, et. al., Journal of Macromolecular Science-Chemistry, Vol. A6,pp. 513-567 (1972) report on the synthesis and chelating properties oflow molecular weight poly(glycidyl methacrylate) reacted withiminoacetic and iminodiacetic acids. Although the D'Alelio polymers havestructural similarities to the instant polymers, they are nonethelesschemically distinct. Significantly, the D'Alelio polymers are esterderivatives and suffer from the same hydolytic instability as the '702compounds. Polymers of the instant invention are stable to hydrolysis inaqueous medium. Therefore, the D'Alelio reference is not consideredpertinent prior art to the instant invention.

Lorenc, U.S. Pat. No. 4,457,847, cites the use of carboxyl containingsequestrant polymers to treat hardness in boiler waters to prevent orremove scale formation on heat transfer surfaces.

DETAILED DESCRIPTION OF THE INVENTION

This invention pertains to novel water-soluble copolymers which containpendant functional groups. Specifically, the novel copolymers of theinvention have the structure of Formula I: ##STR1##wherein E in theabove formula is the repeat unit remaining after polymerization of apolymerizable monomer, containing pendant carboxylic acid orwater-soluble salts thereof, carboxylic amide, lower alkyl (C1-C6)ester,or lower (C1-C6) alkyl hydroxylated ester of such carboxylic acids.Compounds encompassed by E in Formula I include polymerized acrylicacid, methacrylic acid, acrylamide, maleic acid or anhydride, itaconicacid, andthe like.

It is contemplated that E in Formula I also encompasses mixtures ofmonomers, provided that they fall within the definition of E givenabove. One such preferred mixture of monomers is acrylicacid/hydroxypropylacrylate.

R1 in Formula I is an unsubstituted linear or branched lower alkylenegrouphaving from about 1 to about 6 carbon atoms, or an hydroxylsubstituted linear or branched lower alkylene group having from about 1to about 6 carbon atoms. R2 and R3 are chosen independently fromhydrogen, lower alkylene group containing from about 1 to about 5 carbonatoms, hydroxyl substituted lower alkylene group having from about 1 toabout 5 carbon atoms, or carboxyl substituted lower alkylene grouphaving from about 1 toabout 5 carbon atoms. The above substituents arepreferred, but other substituents on the nitrogen capable of chelationare also contemplated. These groups include, but are not limited to,phosphonic acid groups, sulfonic acid groups, and the like.

M and L independently denote hydrogen or a water-soluble cation, e.g.,ammonium, alkali metal, organic aminium ion, and the like. It will bereadily apparent to those skilled in the art that M and L will becations only when R2 and R3 contain groups requiring a cation forelectrical neutrality, such as carboxyl, phosphonic, or sulfonic acidgroups.

The molar ratio of monomers (g:h) in Formula I may fall within the rangeof20:1 to 1:10, with a molar ratio (g:h) of about 10:1 to 1:5 beingpreferred. It is to be understood that molecular weight of the novelcopolymers is less a key criterion than that the copolymers bewater-soluble. Nonetheless, the number-average molecular weight of thenovel water-soluble copolymers of Formula I may fall within the range of1,000 to 1,000,000, with the number average molecular weight within therange of about 1,500 to about 500,000 being preferred, and thenumber-average molecular weight within the range of about 1,500 to about25,000 being most preferred.

The preparation of the monomer(s) designated as (g) in Formula I may bein accordance with well known techniques. For instance, one suchpossible monomer, acrylic acid, may be prepared by hydrolysis ofacrylonitrile or by oxidation of acrolein.

The allyl ether monomer, represented by fragment (h) of Formula I, maybe prepared by a ring-opening reaction of an allylic glycidyl ether withammonia, primary, secondary, or tertiary amines. The ring-openingreactionof amines with the epoxide group of the allylic glycidyl etheris analogousto the ring-opening reaction of allylic glycidyl ethers withreagents such as bisulfites or phosphorous acid, to give sulfonic acids,or salts thereof, or phosphites, respectively, as described thoroughlyin Chen, U.S. Pat. Nos. 4,659,481 and 4,659,480. When R1 in Formula I is--CH₂ --CHOH--CH₂ --, the allylic glycidyl ether precursor is allylglycidyl ether (AGE), the preferred allylic glycidyl ether. The reactionis illustrated with AGE and a secondary amine: ##STR2##

AGE will be used hereinafter as the illustrative allylic glycidyl etherforthe sake of simplicity, but its use hereinafter is not to beconstrued as limiting the invention in any way. For example, amethallylic glycidyl ether will also be useful in the present invention.

In the above equation, R₂, R₃, M, and L have the same meaning asdelineated in Formula I. The following amines, among others, may beemployed in the above reaction: ammonia, methylamine, ethylamine,dimethylamine, diethylamine, propylamine, n-butylamine, isopropylamine,isobutylamine, ethanolamine, propanolamine, etc. It is to be understoodthat the enumeration of the above amines in no way limits the utility ofthe present invention. Those skilled in the art would recognize themyriadamines which could be utilized to synthesize monomers that wouldbe useful for the present invention.

It is also to be understood that hen a tertiary amine is used tosynthesizethe amine-containing monomer in the above reaction, the thirdgroup attached to the nitrogen will be either R2M or R3L, and oneequivalent of an inorganic acid, preferably hydrogen chloride, would beneeded to achieve a stable product, which in the case of a tertiaryamine would be aquaternary ammonium salt. The quaternary ammonium saltwould have a permanent positive charge independent of pH. The inorganicacid, preferably hydrogen chloride, needed when a tertiary amine is usedcould be in any of its readily available forms, i.e., gaseous, aqueoussolution,etc.

The carboxylate-containing amines include, but are not limited to,asparticacid, glycine, sarcosine (n-methyl glycine), iminodiacetic acid(IDA), hydroxyethylglycine, etc. The amines containing carboxylic acidscan be utilized in the acid or the salt form. If desired in the saltform, the carboxylic acids are preferably converted to theirwater-soluble salts with ammonia, organic amines, caustic soda, and thelike (as indicated by M and L in Formula I) prior to reaction with theAGE, but the neutralization could also be conducted after the reactionwith the AGE, oreven after the subsequent polymerization.

The ring opening reaction may be carried out in the absence of solvent,or in a suitable solvent, with water being preferred. The reactiontemperature may range from 0 ° C. to 80 ° C. Alkaline materials can beused in catalytic amounts to speed the reaction, or to drive thereaction to completion. Preferred as the alkaline material is causticsoda, caustic potash, or soda ash.

During the ring opening reaction, trace amounts of the glyceryl compoundmay be formed. This can usually be controlled to less than 5 mole %, andis due to hydrolysis of the AGE according to the equation: ##STR3##

If desired, the hydrolysis product (glyceryl allyl ether, GAE) may beremoved from the mixed monomer solution via the conventional techniquessuch as distillation, solvent extraction, and the like. It is to beunderstood that the method of removal of this, or other impurities, donotin any way limit the practice of our invention. In any case, suchmethods will be known to those skilled in the art.

The present inventors prefer to utilize the monomer containing theimpurities, if any, as it is produced. It may therefore contain minoramounts of GAE. When the GAE is not separated prior to polymerization,it will be incorporated into the polymer along with the primary aminecomponent.

It is to be understood that the above methods of synthesis of the aminecontaining monomer do not limit the methods of preparation of the saidmonomer.

After the desired monomers are produced, and isolated if desired,polymerization is conducted. Radical initiation is the preferred meansof initiation, and the polymerization may be conducted in any of themedia familiar to those skilled in the art, such as solution,suspension, bulk, or emulsion techniques. Any of the well knowninitiators may be used to polymerize the monomers, such as azocompounds, peroxides, redox couples, persulfates, and the like.Likewise, any of the chain transfer agents familiar to those skilled inthe art may be used to control molecular weight. These include, but arenot limited to, lower alkyl alcohols such as isopropanol, amines,mercaptans, and the like. Accelerators such as bisulfite or ascorbicacid may also be used. It is to be understood that the aforementionedpolymerization methods do not in any way limit the synthesis of polymersuseful in our invention. Similarly, the tertiary structure (tacticity,arrangement of monomers in the polymer chain, etc.) of the polymers isnot limiting to our invention.

The formation of polymers was confirmed by the following techniques:viscosity increase; gel permeation chromatography; and carbon-13 nuclearmagnetic resonance (NMR) spectroscopy. The carbon-13 NMR spectra showthe typical broad, polymer-type backbone, with a complex C--C region(35-47 ppm) and C--O--C region (70-75 ppm), with either a trace or nounreacted monomers. Preferred polymers according to our invention arecopolymers of the sodium salt of acrylic acid withallyloxyhydroxypropylamino componentshaving the structure of Formula II:##STR4##wherein the identity of R₂, R₃, M and L for the preferredcopolymers are as shown in Table 1.

                  TABLE 1                                                         ______________________________________                                        Structures of the Copolymers                                                  Copolymer                                                                     Example R.sub.2     R.sub.3      M   L    Mn                                  ______________________________________                                        8       CH.sub.2    CH.sub.2 CH.sub.2 COO/H*                                                                   H   Na/- 2,350                               9       CH.sub.2    CH.sub.2 CH.sub.2 COO/H*                                                                   H   Na/- 3,200                               10      CH.sub.2    CH.sub.2     H   H    2,469                               11      CH.sub.2    CH.sub.2     H   H    2,350                               12      CH.sub.2 COO                                                                              CH.sub.2 COO Na  Na   4,450                               13      CH.sub.2    CH.sub.2 COO H   Na   4,200                               14      CH.sub.2 CH.sub.2 COO                                                                     CH.sub.2 CH.sub.2 COO                                                                      Na  Na   7,000                               ______________________________________                                        *Results from addition reaction of amino component to acrylic acid, giving     terpolymers. For details, see Examples 8 and 9.                          

Mn, number average molecular weight, was measured by gel permeationchromatography (GPC) using Toyo Soda G-2000 SW or G-4000 SW columnscalibrated with polystyrene sulfonate standards in sodium nitratesolution. Molecular weight results from GPC depend on the type ofcolumn, conditions and standards used.

Also preferred are copolymers of sodium methacrylate withallyloxyhydroxy propylamino components (Example 15).

Most preferred are copolymers of acrylic acid with glycine,N-(carboxymethyl)-N-[2-hydroxy-3-(2-propenyloxy)propyl], disodium salt(wherein MR2 and R3L in Formula II are both --CH2--COONa), andcopolymers of methacrylic acid with 2-propanol,1-(diethylamino)-3-(2-propenyloxy), (wherein MR2 and R3L in Formula Iare both --CH2--CH3).

The copolymers of the instant invention may be used alone or incombinationwith other additives to inhibit corrosion and control theformation and deposition of scale imparting compounds in water systems.However, they are not limited to use in any specific category of watersystem. For instance, in addition to boiler and cooling water systems,the copolymers may also be effectively utilized in scrubber systems andthe like wherein corrosion and/or the formation and deposition of scaleforming salts is a problem. Other possible environments in which theinventive copolymers maybe used are for sea water desalinization anddust collecting systems in iron and steel manufacturing. The copolymersare effective in controlling iron-induced fouling in wells or othergroundwater systems. The copolymerswill also be effective in scalecontrol in cooling systems containing high levels of alum or ferricchloride.

The copolymers may also be used to prevent precipitation of calciumcarbonate, calcium sulfate, calcium phosphate, calcium phosphonate,calcium oxalate, barium sulfate, zinc hydroxide, aluminum hydroxide,aluminum oxide, iron oxide, iron hydroxide, ferric chloride, etc. inwatersystems. They will also be useful, for example, as pigmentdispersants, cement dispersants, builders in detergents, and mineralbeneficiation aidssuch as in iron, copper, molybdate mining, etc.

The copolymers of the present invention can also be used with othercomponents in order to enhance the corrosion inhibition and scalecontrolling properties thereof. For instance, the copolymers may be usedin combination with one or more kinds of compounds selected from thegroupconsisting of inorganic phosphates, phosphonic acid salts, organicphosphoric acid esters, and polyvalent metal salts such as those fromzinc, chromate, molybdate, and nickel.

The copolymers may be used in combination with conventional corrosioninhibitors for iron, steel, copper, copper alloys, or other metals,conventional scale and contamination inhibitors, metal ion sequesteringagents, and other conventional water treating agents.

Exemplary corrosion inhibitors comprise chromates, bichromates,tungstates,molybdates, nitrites, borates, silicates, oxycarboxylicacids, amino acids,catechols, aliphatic amino surface-active agents,benzotriazole, and mercapto benzothiazole.

Scale and contamination inhibitors include lignin derivatives, tannicacids, starches, polyacrylic acids, acrylic acid/hydroxyalkylacrylatecopolymers, and acrylic acid/allyloxyhydroxypropylsulfonate copolymers.

Metal ion sequestering agents include ethylenediamine,diethylenetriamine, and the like, and polyaminocarboxylic acidsincluding nitrilotriacetic acid, ethylenediaminetetraacetic acid,diethylenetriaminepentaacetic acid,andhydroxyethylethylenediaminetriacetic acid.

Synergistic effects may occur when the copolymers disclosed in thisinvention are used in combination with the reagents described above.

The novel water soluble copolymers of our invention may contain pendantfunctional amino carboxylic acid groups. These functional groups areconnected to the polymer backbone through the hydrolytically andthermallystable ether linkage. These copolymers have shown uniqueproperties in controlling iron deposition and preventing precipitationof calcium phosphate and calcium carbonate in aqueous systems. The novelcopolymers should also find particularly useful application in boilerwater treatment, whereby their chelating abilities will allow a reduceddosage of chelating agents, which are commonly used in boiler treatmentprograms.Furthermore, the presence of the chelating group permanentlyattached to a polymer chain will minimize the possible corrosion causedby non-bonded chelating agents in various parts of the boiler systems,where corrosion caused by chelating agents could be a problem. Theinvention is further illustrated by the following specific, but notlimiting, examples.

EXAMPLES

Examples 1-7 illustrate the synthesis of the monomers, and Examples 8-15illustrate synthesis of the copolymers. The monomers of Examples 3 and 4have not been previously described, and thus have no CAS Registry No.Likewise, the novel copolymers do not have CAS Registry Nos. Examples ofthe efficacy of the copolymers in aqueous systems are also given.

EXAMPLE 1 Preparation of 2-propanol, 1-(methylamino)-3-(2-propenyloxy)[40987-35-7]

Allyl glycidyl ether (98.5% pure, 196 g, 1.7 mole) was added over aperiod of 130 minutes to methylamine (40% aqueous solution, 198 g, 2.55mole), maintaining a reaction temperature of 35°±4° C. After addition,the reaction mixture was stirred at 35±1° C. for 30 minutes, then heatedat 60±1° C. for 90 minutes. The reaction mixture was then cooled to roomtemperature. 2-Propanol, 1-(methylamino)-3-(2-propenyloxy) was collectedvia vacuum distillation atabout 95° C./3 mm Hg.

EXAMPLE 2 Preparation of 2-propanol,1-(dimethylamino)-3-(2-propenyloxy)[78752-11-1]

Allyl glycidyl ether (98.5% pure, 115 g, 1.0 mole) was added over aperiod of 130 minutes to dimethylamine (60% aqueous solution, 90 g, 1.2mole), maintaining a reaction temperature of 25±2° C. After addition,the reaction mixture was stirred at 30°±3° C. for 30 minutes, thenheated at 50°±2° C. for 120 minutes. The reaction mixture was thencooled to room temperature. 2-Propanol,1-(methylamino)-3-(2-propenyloxy) was collected via vacuum distillationatabout 73° C./4 mm Hg.

EXAMPLE 3 Preparation of Glycine,N-(carboxymethyl)-N-[2-hydroxy-3-(2-propenyloxy) propyl], disodium salt

Iminodiacetic acid (98% pure, 34 g, 0.25 mole) was dispersed in 104 mlDI water at room temperature. Sodium hydroxide (50% aqueous solution, 40g, 0.5 mole) was added over a period of 60 minutes, maintaining areaction temperature of 10±2° C. After addition, the reaction mixturewasstirred at room temperature for 60 minutes.

The resulting disodium iminodiacetate solution (24.9%, 169.3 g, 0.238mole)was added over a period of 85 minutes to a mixture of 34 ml DIwater and allyl glycidyl ether (98.5% pure, 27.55 g, 0.238 mole),maintaining a reaction temperature of 27±3° C. After addition, thereacton mixture was stirred at 30° C. for 70 minutes. Glycine,N-(carboxymethyl)-N-[2-hydroxy-3-(2-propenyloxy) propyl], disodium saltwas recovered as a 30% active solution.

EXAMPLE 4 Preparation of glycine,N-methyl-N-[2-hydroxy-3-(2-propenyloxy)-propyl], monosodium salt

N-methyl glycine (98% pure, 32 g, 0.35 mole) was dispersed in 64 ml DIwater at room temperature. Sodium hydroxide (50% aqueous solution, 28 g,0.35 mole) was added over a period of 80 minutes, maintaining a reactiontemperature of 5°±2° C. After addition, the reaction mixture was stirredat room temperature for 60 minutes.

The resulting sodium N-methyl glycinate solution (31.6%, 123 g, 0.348mole)was added over a period of 70 minutes to a mixture of 33 ml of DIwater andallyl glycidyl ether (98.5% pure, 40.3 g, 0.348 mole),maintaining a reaction temperature of 20±2° C. After addition, thereaction mixture was stirred at 25° C. for 100 minutes. Glycine,N-methyl-N-[2-hydroxy-3-(2-propenyloxy)propyl], monosodium salt wasrecovered as a 40% active aqueous solution.

EXAMPLE 5 Preparation of 2-Propanol, 1-amino-3-(2-propenyloxy)[6967-44-8]

Allyl glycidyl ether (98.5% pure, 185 g, 1.6 mole) was added over aperiod of 225 minutes to ammonium hydroxide (26% ammonia in water, 629g, 9.6 mole), maintaining a reaction temperature of 9°±3° C. Afteraddition, the reaction mixture was stirred at 10° C. for 20 minutes,then room temperature for 45 minutes. 2-Propanol,1-amino-3-(2-propenyloxy) was collected via vacuum distillation at about120° C./10 mm Hg.

EXAMPLE 6 Preparation ofBeta-alanine,N-(2-carboxyethyl)-N-[2-hydroxy-3-(2-propenyloxy)propyl],disodium salt [74988-14-0]

Methyl acrylate (99% pure, 44.2 g, 0.508 mole) was added over a periodof 180 minutes to a mixture of 33 ml methanol and 2-propanol,1-amino-3-(2-propenyloxy) (99.8% pure, 33.4 g, 0.254 mole), maintaininga reaction temperature of 12±3° C. After addition, the reaction mixturewas stirred at room temperature for 11 hours.

48 ml of methanol was added to the resulting beta-alanine,N-(2-carboxyethyl)-N-[2-hydroxy-3-(2-propenyloxy)propyl], dimethyl ester(75%, 92 g, 0.228 mole), and the reaction mixture was cooled to 15°C.Sodium hydroxide (99% pure, 18.5 g, 0.456 mole) was then dissolved inthe reaction mixture, maintaining a reaction temperature below 25° C.After dissolution, the batch was stirred at room temperature for 135minutes. 100 ml of DI water was then added and an exotherm to 31° C. wasobserved. The reaction mixture was stirred at 20° C. for 180minutes,before removing the methanol by vacuum distillation.Beta-alanine,N-(2-carboxymethyl)-N-[2-hydroxy-3-(2-propenyloxy)propyl],disodium salt was recovered as a 56% active aqueous solution.

EXAMPLE 7 Preparation of 2-propanol, 1-(diethylamino)-3-(2-propenyloxy)[14112-80-2]

Allyl glycidyl ether (146 g, 1.25 mole) was added over a period of 120minutes to a solution of diethylamine (97 g, 1.3 mole) in DI water (33ml), maintaining a reaction temperature of 30±10° C. After addition, thebatch was stirred at 35±5 ° C. for 135 minutes, then room temperatureovernight. The batch was then heated at 50±2° C. for 60 minutes before2-propanol, 1-(diethylamino) 3-(2-propenyloxy) was collected via vacuumdistillation at 98° C./3mm Hg.

Syntheses of copolymers with acrylic acid are illustrated in Examples8-14.

EXAMPLE 8 Preparation of acrylic acid/2-propanol,1-(methylamino)-3-(2-propenyloxy)/beta-alanine,N-methyl-N-[2-hydroxy-3-(2-propenyloxy)propyl], terpolymer

2-Propanol, 1-(methylamino)-3-(2-propenyloxy) (Example 1, 12.6 g), water(114.13 g), and isopropyl alcohol (32.09 g) were charged to a suitablereactor and purged with nitrogen. Sodium persulfate (22% aqueoussolution,15.73 g) and acrylic acid (36.77 g) were simultaneously addedover a 4 hourperiod, maintaining a reaction temperature of 87±4° C.After addition, the reaction mixture was held at 91° C. for 1 hour. Theresidual isopropyl alcohol was then removed by azeotropic distillation.Sodium hydroxide (50% aqueous solution, 20 g) and 119 ml of water werethen added, maintaining the temperature below 40° C.

Under the polymerization conditions, some addition reaction between thesecondary amino hydrogen and the free acrylic acid occurred. This wasevidenced by the 13 C NMR spectroscopy which indicated a mole ratio ofacrylic acid/2-propanol, 1-(methylamino)-3-(2-propenyloxy)/beta-alanine,N-methyl-N-[2-hydroxy-3-(2-propenyloxyl)propyl] of 15.6:1.0:1.9respectively. This corresponds to about 65% of the available amineformingthe adduct with acrylic acid.

EXAMPLE 9 Preparation of acrylic acid/2-propanol,1-(methylamino)-3-(2-propenyloxy)/beta-alanine,N-methyl-N-[2-hydroxy-3-(2-propenyloxy)propyl] terpolymer

Prepared as described in Example 8 except less isopropyl alcohol (19.75g) and less water (21.59 g) were utilized in the polymerization. Thisresulted in a higher molecular weight. 13C NMR analysis of the productwassimilar to that obtained for Example 8, confirming the terpolymerstructure.

EXAMPLE 10 Preparation of acrylic acid/2-propanol,1-(dimethylamino)-3-(2-propenyloxy)copolymer

Prepared as described in Example 8 utilizing 2-propanol,1-(dimethylamino)-3-(2-propenyloxy) (Example 2, 13.68 g), water (91.82g),isopropyl alcohol (21.59 g), sodium persulfate (22% aqueous solution,16.05g), and acrylic acid (36.76 g). The hold period after addition waslengthened to 2 hours. After distillation, sodium hydroxide (50% aqueoussolution, 20 g) and 119 ml of water were added.

EXAMPLE 11 Preparation of acrylic acid/2-propanol,1-(dimethylamino)-3-(2-propenyloxy)copolymer

Prepared as described in Example 10 utilizing 2-propanol,1-(dimethylamino)-3-(2-propenyloxy) (Example 2, 20.52 g), water (105.88g), isopropyl alcohol (22.91 g), sodium persulfate (22% aqueoussolution, 18.23 g), and acrylic acid (36.76 g). After distillation,sodium hydroxide(50% aqueous solution, 20 g) and 130 ml of water wereadded.

EXAMPLE 12 Preparation of acrylic acid/glycine,N-(carboxymethyl)-N-[2-hydroxy-3-(2-propenyloxy) propyl], disodium saltcopolymer

Prepared as described in Example 10 utilizing glycine,N-(carboxymethyl)-N-[2-hydroxy-3-(2-propenyloxy)propyl], disodium saltsolution (Example 3, 97.04 g), water (105.45 g), isopropyl alcohol(19.54 g), sodium persulfate (22.8% aqueous solution 20 g), and acrylicacid (36.77 g). One hour after addition, tert-butylhydroperoxide (70%aqueous solution, 0.456 g) was added. After distillation, sodiumhydroxide (50% aqueous solution, 12 g) and 1 ml of water were added.

EXAMPLE 13 Preparation of acrylic acid/glycine,N-methyl-N-[2-hydroxy-3-(2-propenyloxy)propyl], monosodium saltcopolymer

Prepared as described in Example 12 utilizing glycine,N-methyl-N-[2-hydroxy-3(2-propenyloxy)propyl] monosodium salt solution(Example 4, 56.29 g), water (106.22 g), isopropyl alcohol (31.32 g),sodium persulfate (20.5% aqueous solution, 20 g), acrylic acid (36.77g), and tert-butylhydroperoxide (70% aqueous solution, 0.418 g). Theaddition period was lengthened to 5 hours. After distillation, sodiumhydroxide (50% aqueous solution, 16 g) and 110 ml of water were added.

EXAMPLE 14 Preparation of acrylic acid/beta-alanine,N-(2-carboxyethyl)-N-[2-hydroxy-3-(2-propenyloxy)propyl], disodium saltcopolymer

Prepared similarly to Example 10 utilizing beta-alanine,N-(2-carboxyethyl)-N-[2-hydroxy-3-(2-propenyloxy)propyl], disodium saltsolution (example 6, 30.00 g , water (63.17 g), isopropyl alcohol (21.30g), sodium persulfate (25% aqueous solution, 12.08 g), acrylic acid(23.34g), tert-butylhydroperoxide (70% aqueous solution, 0.58 g), andsodium hydroxide (50% aqueous solution, 8.47 g). For thispolymerization, the sodium hydroxide was charged simultaneously with theacrylic acid and the sodium persulfate solution; the addition period wasshortened to 3 hours; the hold period was lengthened to 3 hours; and thetert-butylhydroperoxidewas added 2 hours after addition. Afterdistillation, 95 ml of water was added.

Example 15 illustrates the preparation of a copolymer of methacrylicacid with the product of Example 7.

EXAMPLE 15 Preparation of methacrylic acid/2-propanol,1-(diethylamino)-3-(2-propenyloxy) copolymer

2-Propanol, 1-(diethylamino)-3-(2-propenyloxy) (Example 7, 16 g, 0.083mole) and 171 ml DI water were charged to a suitable reactor and purgedwith nitrogen. Sodium persulfate (20.5% aqueous solution, 20 g) andmethacrylic acid (44 g, 0.5 mole) were simultaneously added over a 4hour period, maintaining a batch temperature of 90±2° C. 50% aqueoussodium hydroxide (7 g total) was charged during the addition period asneeded to maintain polymer solubility. After addition, the batch washeld at 90±2° C. for 1.5 hours. After the hold period, 50% sodiumhydroxide (29 g) was charged, maintaining the batch temperature below30° C.

Table II presents a summary of the physical properties of the copolymersproduced in accordance with Examples 8-15.

                                      TABLE II                                    __________________________________________________________________________    Physical Properties of the Copolymers (g/h)                                                     Charge                                                      Co-  Monomer                                                                              Monomer                                                                             Mole Ratio                                                                          Brookfield.sup.a                                      polymer                                                                            (g)    (h)   g:h   Viscosity                                                                           pH  Mn.sup.b                                    __________________________________________________________________________    Ex 8 Acrylic                                                                              Ex 1  6:1   13.5  5.5 2,350                                            Acid                                                                     Ex 9 "      Ex 1  6:1   15.6  5.5 3,200                                       Ex 10                                                                              "      Ex 2  6:1   21.8  5.5 2,469                                       Ex 11                                                                              "      Ex 2  4:1   26.3  5.7 2,350                                       Ex 12                                                                              "      Ex 3  5:1   21.5  4.9 4,450                                       Ex 13                                                                              "      Ex 4  5:1   17.5  5.1 4,200                                       Ex 14                                                                              "      Ex 6  6:1   13.4  5.2 --                                          Ex 15                                                                              Methacrylic                                                                          Ex 7  6:1   38.4  9.65                                                                              --                                               Acid                                                                     __________________________________________________________________________     .sup.a 25% solutions @ 25° C.                                          .sup.b Number average molecular weight                                   

Table III illustrates the excellent activity of the novel copolymers fordeposit control in aqueous systems containing high levels of well wateriron. The results are given as percent of soluble iron remaining insolution after specified times. The higher the percent soluble iron, themore effective the scale control of the polymer.

                                      TABLE III                                   __________________________________________________________________________    Deposit Control Activity                                                      Well Water Iron Results                                                       Percent Soluble Iron                                                          Conditions:                                                                         200 ppm Ca .sup.2+ as CaCO.sub.3 ; 100 ppm Mg.sup.2+ as CaCO.sub.3            ;                                                                             8 ppm Fe.sup.+2 ; pH 8; 45°  C.; 0, 24, 48, 72 hour                    equilibration                                                           Treatment                                                                           Treatment Conc                                                          Copolymer                                                                           (ppm active)                                                                            0 hour                                                                             24 hour                                                                             48 hour                                                                             72 hour                                      __________________________________________________________________________    Control         1.85 1.20  1.00  1.00                                         Example 8                                                                           10.00     8.80 1.60  1.00  3.70                                               20.00     96.20                                                                              96.30 81.60 96.20                                              40.00     97.40                                                                              95.50 83.70 97.50                                        Example 9                                                                           10.00     18.70                                                                              1.10  1.00  3.50                                               20.00     96.60                                                                              96.10 82.42 97.20                                              40.00     96.80                                                                              95.60 81.60 97.50                                        Example 10                                                                          10.00     10.80                                                                              1.20  1.00  2.00                                               20.00     95.50                                                                              70.90 22.70 35.60                                              40.00     96.40                                                                              97.10 81.25 97.50                                        Example 11                                                                          10.00     2.80 1.40  1.00  2.00                                               20.00     96.30                                                                              71.80 79.10 88.30                                              40.00     96.40                                                                              97.10 81.25 97.50                                        __________________________________________________________________________

Table IV illustrates that the copolymers are effective in inhibiting theformation of calcium phosphate, commonly encountered in industrial watersystems, such as cooling water systems.

                  TABLE IV                                                        ______________________________________                                        Calcium Phosphate Inhibition                                                  Conditions:                                                                           600 ppm Ca.sup.2+  as CaCO.sub.3, 12 ppm PO.sub.4.sup.-3, 2 mM                NaHCO.sub.3,                                                                  pH 7.0, 70° C., 18 hour equilibration                                  % Inhibition                                                          Treatment                                                                              Treatment   Concentrations                                                                            (ppm active)                                 Copolymer                                                                              5           10          20                                           ______________________________________                                        Example                                                                              8     9.6         11.3      39.6                                              9     11.3        10.9      76.1                                              10    5.4         9.2       35.6                                              11    4.0         9.4       70.9                                              12    3.7         3.7       9.1                                               13    8.6         2.7       11.2                                              14    5.6         13.5      38.2                                       ______________________________________                                    

Table V demonstrates the excellent activity of the novel copolymers ininhibiting the formation of calcium carbonate, another commonlyencountered scale-forming agent in various industrial water systems.

                  TABLE V                                                         ______________________________________                                        Calcium Carbonate Inhibition                                                  Conditions:                                                                           1105 ppm Ca.sup.2+ as CaCO.sub.3, 1170 ppm CO.sub.3.sup.-2 as                 CaCO.sub.3                                                                    pH 9.0, 70° C., 18 hours equilibration, LSI = 3.67                     % Inhibition                                                          Treatment                                                                              Treatment  Concentrations                                                                            (ppm active)                                  Copolymer                                                                              0.5        1.0         2.0                                           ______________________________________                                        Example                                                                              8     0.0        23.4      37.5                                               9     5.8        29.5      39.4                                               10    0.0        18.0      34.6                                               11    0.0        10.5      33.6                                               12    6.3        31.8      44.6                                               13    8.3        31.0      43.0                                               14    8.5        35.9      50.2                                        ______________________________________                                    

Tables VI and VII show that the copolymers are less effective indispersingferric oxide or montmorillonite clay.

                  TABLE VI                                                        ______________________________________                                        Ferric Oxide Dispersion                                                       Conditions:                                                                           300 ppm Fe.sub.2 O.sub.3, 200 ppm Ca.sup.2+ as CaCO.sub.3, 1 mM               NaCl,                                                                         10 mM NaHCO.sub.3, pH 7.0, 45° C., 18 hours settling                  % Transmittance                                                        Treatment                                                                              Treatment  Concentrations                                                                            (ppm active)                                  Copolymer                                                                              2.5        5.0         10.0                                          ______________________________________                                        Example                                                                              8     1.5        2.5       4.3                                                9     3.0        4.5       5.0                                                10    1.5        1.5       1.5                                                11    1.5        1.5       2.0                                                12    9.0        15.0      26.0                                               13    2.5        5.5       5.5                                                14    5.5        9.0       20.5                                        ______________________________________                                    

                  TABLE VII                                                       ______________________________________                                        Montmorillonite Dispersions                                                   Conditions:                                                                           200 ppm Ca.sup.2+ as CaCO.sub.3, pH 7.0, 1000 ppm                             montmorillonite, 18 hours equilibration                                      % Transmittance                                                        Treatment                                                                              Treatment  Concentrations                                                                            (ppm active)                                  Copolymer                                                                              5          10          20                                            ______________________________________                                        Example                                                                              8     0.0        0.0       0.0                                                9     0.0        0.0       0.0                                                10    0.0        0.0       0.0                                                11    0.0        0.0       0.0                                         ______________________________________                                    

Table VIII demonstrates the scale control in a boiler water system of amethacrylic acid copolymer (Example 15) in a phosphate precipitationprogram. Details of typical boiler test condition can be found in U.S.Pat. No. 4,659,481, col. 17.

                  TABLE VIII                                                      ______________________________________                                        Boiler Scale Reduction                                                        Precipitating Phosphate Program                                               900 psig; 4 ppm Ca, 1 ppm Mg (as CaCO.sub.3)                                  15 cycles                                                                                          Deposit                                                                       Weight      % Scale                                      Polymer  Conc.(ppm)  Density(g/ft2)                                                                            Reduction                                    ______________________________________                                        None     --          8.15        --                                           Ex. 15   2.5         0.99        88                                           Ex. 15   5.0         0.22        97                                           ______________________________________                                        % Scale reduction is calculated from the equation:                             ##STR5##                                                                     where DWD is Deposit Weight Density                                           control is the boiler test without polymer                                

It is to be understood that the above boiler studies in no way limit theutility of the present invention for other boiler treatment programs,suchas polymer/phosphate/chelant, coordinated phosphate, etc.

While this invention has been described with respect to particularembodiments thereof, it is apparent that numerous other forms andmodifications of this invention will be obvious to those skilled in theart. The appended claims and this invention generally should beconstrued to cover all such obvious forms and modifications which arewithin the true spirit and scope of the present invention.

We claim:
 1. Composition comprising a water soluble polymer, saidpolymer comprising repeat unit moieties (g) and (h) having thestructure: ##STR6## wherein E in the above formula is the repeat unitremaining after polymerization of a polymerizable monomer or monomers,and wherein R1 in the above formula comprises a C1-C6 linear or branchedalkylene or substituted alkylene, R2 and R3 independently representhydrogen, C1-C5 lower alkylene or substituted lower alkylene, and M andL, when required, independently represent hydrogen or a water-solublecation.
 2. Composition according to claim 1, wherein E is the repeatunit after polymerization of a polymerizable carboxylic acid, loweralkyl (C1-C6) ester of said carboxylic acid, or lower (C1-C6) alkylhydroxylated ester of said carboxylic acid.
 3. Composition according toclaim 1, wherein E is the repeat unit after polymerization of acrylic ormethacrylic acid.
 4. Composition according to claim 1, wherein E is therepeat unit after polymerization of maleic acid or anhydride. 5.Composition according to claim 1, wherein E is the repeat unit afterpolymerization of itaconic acid.
 6. Composition according to claim 1,wherein E is the repeat unit after polymerization of acrylamide. 7.Composition according to claim 1, wherein E is the repeat unit afterpolymerization of hydroxypropylacrylate.
 8. Composition according toclaim 1, where E is the repeat unit after polymerization ofhydroxyethylacrylate.
 9. Composition according to claim 1, wherein E isthe repeat unit after polymerization of a mixture of polymerizablemonomers.
 10. Composition according to claim 9, wherein E is the repeatunit after polymerization of a mixture of acrylic acid andhydroxypropylacrylate.
 11. Composition according to claim 9, wherein Eis the repeat unit after polymerization of a mixture of acrylic andmethacrylic acids.
 12. Composition according to claim 1, wherein R1 isan unsubstituted lower (C1-C6) alkylene group, or an hydroxylsubstituted lower (C1-C6) alkylene group.
 13. Composition according toclaim 12, wherein R1 is a trimethylene (--CH₂ --CH₂ --CH₂ --) group. 14.Composition according to claim 1, wherein R1 is a --CH₂ --CHOH--CH₂ --group.
 15. Composition according to claim 1, wherein R₂ and R₃ areindependently chosen from hydrogen, lower (C1-C5) alkyl, hydroxysubstituted lower (C1-C5) alkyl, or carboxy substituted lower (C1-C5)alkyl groups, and wherein M and L, when required, are independentlychosen from hydrogen or a water soluble cation.
 16. Compositionaccording to claim 15, wherein R₂ and R₃ are both --CH₂ --COO--, and Mand L are both hydrogen.
 17. Composition according to claim 15, whereinR₂ and R₃ are both --CH₂ --COO--, and M and L are both Na+. 18.Composition according to claim 15, wherein R₂ and R₃ are both --CH₂--CH₂ --, and M and L are both hydrogen.
 19. Composition according toclaim 1, wherein E is the repeat unit from the polymerization of acrylicacid, R₁ is --CH₂ --CHOH--CH₂ --, and MR₂ and R₃ L are both --CH₂--COOH.
 20. Composition according to claim 1, wherein E is the repeatunit from the polymerization of sodium acrylate, R₁ is --CH₂ --CHOH--CH₂--, and MR₂ and R₃ L are both --CH₂ --COONa.
 21. Composition accordingto claim 1, wherein E is the repeat unit from the polymerization ofmethacrylic acid, R₁ is --CH₂ --CHOH--CH₂ --, and MR₂ and R₃ L are both--CH₂ --CH₃.
 22. Composition according to claim 1, wherein E is therepeat unit from the polymerization of sodium methacrylate, R₁ is --CH₂--CHOH--CH₂ --, and MR₂ and R₃ L are both --CH₂ --CH₃.
 23. Compositionaccording to claim 1, wherein the mole ratio of repeat unit moiety (g)to repeat unit moiety (h) is about 20:1 to about 1:10.
 24. Compositionaccording to claim 1, wherein the mole ratio of repeat unit moiety (g)to repeat unit moiety (h) is about 10:1 to about 1:5.
 25. Compositionaccording to claim 1, wherein the mole ratio of repeat unit moiety (g)to repeat unit moiety (h) is about 10:1 to about 2:1.
 26. Compositionaccording to claim 1, wherein the number-average molecular weight of thewater soluble polymer is about 1,000 to about 1,000,000.
 27. Compositionaccording to claim 1, wherein the number-average molecular weight of thewater soluble polymer is about 1,500 to about 500,000.
 28. Compositionaccording to claim 1, wherein the number-average molecular weight of thewater soluble polymer is about 1,500 to about 25,000.